Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest

Margarita E. Aliaga, William Tiznado, Bruce K. Cassels, Marco T. Nuñez, Daniela Millán, Edwin G. Pérez, Olimpo García-Beltrán, Paulina Pavez

Resultado de la investigación: Contribución a una revistaArtículo

5 Citas (Scopus)

Resumen

The Michael addition reactions of the biothiols cysteine, homocysteine, cysteinyl-glycine, γ-glutamyl-cysteine and glutathione with 3-cinnamoylcoumarin derivatives (ChC1-ChC4) in aqueous solution (30 °C, ionic strength 0.2 M KCl) were followed fluorimetrically and evaluated kinetically. The study was completed with a theoretical analysis based on the inverse of the Fukui potential (1/νf (r)), which is proposed for the first time as a local softness descriptor. Thus, considering both experimental results and theoretical analysis, the following conclusions can be drawn: (i) the reactivity of the tested probes towards Michael addition increases in the para-substitution sequence: H < OEt < SMe < Br < NO2, and is not correlated with the σP values of the substituents; (ii) in turn, the descriptor proposed here as local softness (1/νf (r)) appears as a promising reactivity index that is able to explain the higher kN values found for both electron-withdrawing and electron-donating groups; (iii) the nucleophilic reactivity of the biothiols employed increases in the sequence Cys-Gly < Hcy < GSH < Cys < γ-Glu-Cys; and also finally (iv) we have demonstrated that these probes can be used for fluorimetric thiol determination in SH-SY5Y cells.

Idioma originalInglés
Páginas (desde-hasta)697-704
Número de páginas8
PublicaciónRSC Advances
Volumen4
N.º2
DOI
EstadoPublicada - 2014

Áreas temáticas de ASJC Scopus

  • Ingeniería química (todo)
  • Química (todo)

Huella Profundice en los temas de investigación de 'Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest'. En conjunto forman una huella única.

  • Citar esto

    Aliaga, M. E., Tiznado, W., Cassels, B. K., Nuñez, M. T., Millán, D., Pérez, E. G., García-Beltrán, O., & Pavez, P. (2014). Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest. RSC Advances, 4(2), 697-704. https://doi.org/10.1039/c3ra44695f